Azo dyes having a quaternized heterocyclic diazo component radical and an optionally substituted aryloxyalkyl substituent on the amino group of the coupling component radical

ABSTRACT

Basic dyes free from sulfo groups of the formula ##STR1## in which Q signifies an unsubstituted or substituted phenyl or naphthyl radical, 
     R 1  and R 2  signify hydrogen, unsubstituted or substituted alkyl, phenyl or cycloalkyl, 
     R 3  signifies hydrogen, unsubstituted or substituted alkyl or phenyl, 
     the Z containing group signifies a heterocyclic diazo radical containing a quaternary ammonium group, 
     R 4  signifies unsubstituted or substituted alkyl, alkenyl, cycloalkyl or alkoxy, 
     x signifies 1 to 3, 
     A⊖ signifies an anion, and 
     D signifies an unsubstituted or substituted phenylene or naphthylene radical are useful for dyeing and printing homo- and co-polymers of acrylonitrile and asymmetrical dicyanoethylene and synthetic polyamides and polyesters modified to contain acid groups. The obtained dyeings are level and fast to light and wet treatments.

This application is a continuation of application Ser. No. 383,782,filed July 30, 1973 and now abandoned.

The invention relates to basic azo compounds free from sulphonic acidgroups.

The invention provides compounds of formula I, ##STR2## in which Qsignifies a radical of the formula ##STR3## R signifies hydrogen;hydroxy; halogen; alkyl or alkoxy of 1 to 4 carbon atoms, unsubstitutedor substituted by halogen, hydroxy, cyano, phenyl or phenoxy; cycloalkylof 5 or 6 carbon atoms, unsubstituted or substituted by alkyl of 1 to 4carbon atoms; cyano; nitro; trihalomethyl; trifluoromethyl; phenoxy;naphthyloxy, phenylazo; or a radical of the formula --CORo, ##STR4##--SO₂ --Ro, --SO₂ --NH--Ro, ##STR5## --O--CO--NH--Ro, --O--CO--N(Ro)₂,--SO₂ --N(Ro)₂, --CO--NH--Ro,--OSO₂ N(Ro)₂, --CO--N(Ro)₂, --NH--CO--Ro,##STR6## in which the Ro's, independently, signify C₁₋₄ alkyl or phenyl,and X signifies --CO-- or --SO₂ --;

R₁ and R₂, which may be the same or different, signify hydrogen; alkylof 1 to 4 carbon atoms, unsubstituted or substituted by halogen, C₁₋₄alkoxy or phenoxy; phenyl; or C₅₋₆ cycloalkyl;

R₃ signifies hydrogen; alkyl of 1 to 12 carbon atoms, unsubstituted orsubstituted by halogen, hydroxy, cyano, phenyl, phenoxy, C₁₋₄alkoxycarbonyl, C₁₋₄ alkylcarbonyloxy, C₁₋₄ alkoxy, phenylcarbonyloxy(benzoyloxy), ##STR7## or --CON(Ra)₂ in which the Ra's, independently,signify hydrogen or C₁₋₄ alkyl; or phenyl;

Z signifies a residue which together with the nitrogen atom forms anunsaturated heterocyclic ring containing at least five ring atoms, whichmay be carbon, oxygen, sulphur or further nitrogen atoms, which ringoptionally has an aromatic carbocyclic or heterocyclic ring fusedthereto and is, along with any ring fused thereto, optionallysubstituted by substituents selected from alkyl of 1 to 4 carbon atomsand alkoxy of 1 to 4 carbon atoms, each unsubstituted or substituted byphenyl, hydroxy, --CONH₂, cycloalkyl of 5 or 6 carbon atoms, cyano orhalogen; cycloalkyl of 5 or 6 carbon atoms, unsubstituted or substitutedby C₁₋₄ alkyl, C₁₋₄ alkoxy or halogen; phenyl or phenoxy, eachunsubstituted or substituted by cyano, nitro, C₁₋₄ alkyl, C₁₋₄ alkoxy orhalogen; halogen; nitro; cyano; trifluoromethyl; a radical of theformula --CO--Ro, ##STR8## --NH--SO₂ --Ro, --CO--NHRo, --CO--N(Ro)₂,--NH--CO--Ro, --SO₂ --Ro, --SO₂ --N(Ro)₂ or --SO₂ --NHRo, in which Ro isas defined above; or phenylazo; the ##STR9## group being free fromwater-solubilizing groups and containing at least one quaternarynitrogen atom, and being bound to the azo group through a carbon atom,

R₄ signifies a C₁₋₈ alkyl, C₂₋₈ alkenyl or C₁₋₄ alkoxy radical, eachunsubstituted or substituted by halogen, hydroxy, cyano, phenyl,phenoxy, cycloalkyl of 5 or 6 carbon atoms, alkoxy of 1 to 4 carbonatoms or the group --CONH₂ ; or a cycloalkyl radical of 5 or 6 carbonatoms, unsubstituted or substituted by C₁₋₄ alkyl; or the group##STR10## y signifies 1, 2, 3, 4 or 5, and, where y signifies 2 or more,the R's may be the same or different,

x signifies 1, 2 or 3,

A.sup.⊖ signifies an organic or inorganic anion, and

D signifies a phenylene or naphthylene radical, each furtherunsubstituted or further substituted by 1 or 2 substituents selectedfrom C₁₋₄ alkoxy, C₁₋₄ alkyl and halogen.

Any heterocyclic ring in ##STR11## is preferably of 5 or 6 ring atomsand preferably contains 1, 2 or 3 heteroatoms.

As examples of radicals ##STR12## may be given thiazolyl, isothiazolyl,thiadiazolyl, triazolyl, imidazolyl, indazolyl, oxazolyl, pyridinyl,pyrimidinyl, pyridazinyl, pyrazinyl, benzothiazolyl, oxadiazolyl,quinoxalinyl, cinnolinyl, quinolinyl, phthalazinyl, pyrazolyl,benzoxazolyl and benzimidazolyl derivatives.

Preferred examples of ##STR13## are the triazolyl, pyridinyl,benzothiazolyl, quinolinyl and indazolyl derivatives, more preferablythe triazolyl, pyridinyl and benzothiazolyl derivatives and mostpreferably the triazolyl derivatives.

In the compounds of formula I, where Q signifies a naphthalene radical,such radical is preferably unsubstituted.

The preferred compounds of Formula I are those wherein

R₁ is hydrogen, C₁₋₄ alkyl or phenyl,

R₂ is hydrogen,

R₃ is hydrogen; C₁₋₄ alkyl or C₁₋₄ alkyl substituted by phenoxy, phenyl,C₁₋₄ alkoxycarbonyl or benzoyloxy,

R₄ is C₁₋₄ alkyl; C₁₋₄ alkyl substituted by phenyl, hydroxy or --CONH₂ ;or C₁₋₄ alkoxy, ##STR14## is a triazolyl, pyridyl, benzothiazolyl,quinolyl or indazolyl derivative, preferably a triazolyl, pyridyl orbenzothiazolyl derivative, most preferably a triazolyl derivative,

D is phenylene, naphthylene or phenylene substituted in a position orthoto the azo radical by C₁₋₄ alkyl, C₁₋₄ alkoxy or halo, and

Q is phenyl, naphthyl, phenyl substituted by 1 or 2 R's or phenylsubstituted by 3, 4 or 5 halo substituents.

As examples of anions A.sup.⊖ may be given the halides, such aschloride, bromide or iodide, sulphate, bisulfate, methylsulphate,aminosulphate, perchlorate, carbonate, bicarbonate, phosphate,phosphormolybdate, phosphortungstenate, phosphortungstenmolybdate,formate, benzenesulphonate, naphthalenesulphonate,4-chlorobenzenesulphonate, oxalate, maleinate, acetate, propionate,lactate, succinate, chloroacetate, tartrate, malate, methanesulphonateor benzoate ions, or complex anions such as zinc chloride double salts,e.g. ZnCl₃.sup.⊖. The preferred anions are the halide preferablychloride, methylsulphate ZnCl₃.sup.⊖ and acetate ions.

Even more preferred are the compounds of Formula I wherein

R₁ is hydrogen, methyl or phenyl,

R₂ is hydrogen,

R₃ is methyl, ethyl, butyl, phenoxyethyl, benzyl, ethoxycarbonylethyl orbenzoyloxyethyl,

R₄ is methyl, ethyl, benzyl, 2-hydroxyethyl, 2-hydroxypropyl,2-carbamoylethyl or methoxy, ##STR15## is a triazolyl, pyridyl orbenzothiazolyl derivative, especially a triazolyl derivative,

D is phenylene, naphthylene or phenylene substituted in a position orthoto the azo radical by methyl, methoxy or chloro,

Q is phenyl, naphthyl, phenyl substituted by 3, 4 or 5 chlorosubstituents or phenyl substituted by 1 or 2 substituents selected fromchloro, C₁₋₄ alkyl, benzyl, nitro, cyano, phenylsulfonyl,methylsulfamoyl, dimethylsulfamoyl, trifluoromethyl, methoxycarbonyl,methylcarbamoyl, methoxy, phenoxy, benzoyloxy, phenylazo, benzamido,phenylcarbamoyloxy, dimethylcarbamoyloxy, N-methyl-N-phenylcarbamoyloxy,methylsulfonyl, dimethylsulfamoyloxy, phenoxymethyl, benzoyl or hydroxy(especially phenyl, naphthyl, phenyl substituted by 2, 3, 4 or 5 chlorosubstituents, phenyl monosubstituted by one of the aforementionedsubstituents or phenyl substituted by hydroxy and by benzoyl), and x is1 or 2.

Thus, the preferred compounds of Formula I' when P is a group of Formula(a), or an isomer thereof of formula (b) or (c), are those wherein

R₈ is C₁₋₄ alkyl or C₁₋₄ alkyl substituted by phenyl, hydroxy orcarbamoyl,

R₉ is C₁₋₄ alkyl or C₁₋₄ alkyl substituted by phenyl, hydroxy orcarbamoyl, and

R₁₀ is hydrogen, C₁₋₄ alkyl or C₁₋₄ alkyl substituted by phenyl,

especially those of the group wherein

R'₁ is hydrogen or C₁₋₄ alkyl,

R'₂ is hydrogen,

R'₃ is C₁₋₄ alkyl or C₁₋₄ alkyl substituted by phenoxy,

R'₇ is hydrogen, C₁₋₄ alkyl or C₁₋₄ alkoxy,

B is 1,4-phenylene,

Q' is phenyl, naphthyl, phenyl substituted by 3, 4 or 5 chlorosubstituents or phenyl substituted by 1 or 2 substituents selected fromhalo, nitro, cyano, phenylsulfonyl, C₁₋₄ alkylsulfamoyl, di-(C₁₋₄alkyl)sulfamoyl, (C₁₋₄ alkoxy)carbonyl, (C₁₋₄ alkyl)carbamoyl, C₁₋₄alkoxy, benzoyl, phenoxy, benzoyloxy, phenylazo, benzamido,phenylcarbamoyloxy, di-(C₁₋₄ alkyl)carbamoyloxy, N-C₁₋₄alkyl-N-phenylcarbamoyloxy, C₁₋₄ alkylsulfonyl, di-(C₁₋₄alkyl)sulfamoyloxy, trifluoromethyl, C₁₋₄ alkyl or phenyl(C₁₋₄ alkyl),and

x is 1,

and particularly those of the immediately preceding group whereinA.sup.⊖ is chloride, ZnCl₃.sup.⊖, methylsulfate or acetate or wherein

R₈ is methyl,

R₉ is methyl, and

R₁₀ is hydrogen.

Even more preferred compounds of Formula I' when P is a group of Formula(a), or an isomer thereof of Formula (b) or (c), are those wherein

R'₁ is hydrogen or C₁₋₄ alkyl,

R'₂ is hydrogen,

R'₃ is methyl or ethyl,

R'₇ is hydrogen

R₈ is methyl,

R₉ is methyl,

R₁₀ is hydrogen,

B is 1,4-phenylene,

Q' is phenyl, 2-naphthyl, phenyl substituted by 1 to 5 chlorosubstituents or phenyl monosubstituted by nitro, cyano, phenylsulfonyl,methylsulfamoyl, dimethylsulfamoyl, methoxycarbonyl, methylcarbamoyl,methoxy, phenoxy, benzoyloxy, phenylazo, benzamido, phenylcarbamoyloxy,dimethylcarbamoyloxy, N-methyl-N-phenylcarbamoyloxy, methylsulfonyl,dimethylsulfamoyloxy, trifluoromethyl, methyl or benzyl (especiallythose wherein when Q' is monosubstituted phenyl, the substituent is inthe para position), and

x is 1,

especially those of this group wherein A.sup.⊖ is chloride, ZnCl₃.sup.⊖,methylsulfate or acetate.

The invention also provides a process for the production of compounds offormula I, characterised by quaternising a compound of formula II,##STR16## in which Z, D, R₁, R₂, R₃ x and Q are as defined above, byreaction with a compound of formula III,

    R.sub.4 --A                                                III

in which R₄ is as defined above, and A corresponds to A.sup.⊖, above, orby addition reaction of an R₄ yielding epoxide or vinyl compound with acompound of formula II, in the presence of water and with neutralizationemploying an acid HA.

The quaternisation with a compound of formula III may be carried out inconventional manner. Suitably, the reaction is carried out in an inertsolvent, in an aqueous suspension or, where liquid under the reactionconditions, in an excess of the compound of formula III. Wherenecessary, the reaction can be carried out at elevated temperatures andin a buffered medium. As examples of preferred quaternising agents offormula III may be given methyl or ethyl chloride, bromide or iodide,alkyl sulphates, such as dimethyl sulphate, or benzyl chloride. Asexamples of other quaternising agents may be given acrylic acid amidehydrochloride, such as CH₂ ═CH--CO--NH₂ /HCl, chloroacetic acid amide,or epoxides such as ethylene oxide and propylene oxide, andepichlorohydrins, in the presence of an acid of the formula HA.

Preferred compounds of formula I are compounds of formula I', ##STR17##in which P signifies a radical of the formula ##STR18## in which R₈signifies an alkyl radical of 1 to 4 carbon atoms or alkenyl radical of2 to 4 carbon atoms, unsubstituted or substituted by hydroxy, halogen,cyano, phenyl or the group --CONH₂ ; or a cyclohexyl radical,unsubstituted or substituted by C₁₋₄ alkyl,

R₉ signifies an alkyl radical of 1 to 4 carbon atoms, unsubstituted orsubstituted by hydroxy, halogen, cyano, phenyl or the group --CONH₂ ; acyclohexyl radical, unsubstituted or substituted by C₁₋₄ alkyl; or aphenyl radical, unsubstituted or substituted by halogen, C₁₋₄ alkyl orC₁₋₄ alkoxy,

R₁₀ signifies hydrogen or one of the significances of R₉, above, aradical of the formula ##STR19## in which R₁₁ signifies C₁₋₄ alkoxy,C₁₋₄ alkyl or C₂₋₄ alkenyl, each unsubstituted or substituted byhydroxy, halogen, cyano, phenyl or the group --CONH₂,

R₁₂ signifies phenyl; halogen; nitro; cyano; C₁₋₄ alkyl or C₁₋₄ alkoxy;

q signifies 0, 1 or 2; and where q signifies 2, the R₁₂ 's may be thesame or different, a radical of the formula ##STR20## in which R₁₃signifies a C₁₋₄ alkyl radical, R₁₄ signifies halogen, nitro, cyano,trifluoromethyl, C₁₋₄ alkylsulphonyl or, di-(C₁₋₁₄ alkyl)sulfamoyl orphenylsulphonyl,

R₁₁ is as defined above, and

q is a defined above, and when q signifies 2, the R₁₄ 's may be the sameor different;

a radical of the formula ##STR21## in which R₈, R₉, R₁₄ and q are asdefined above; and when q signifies 2, the R₁₄ 's may be the same ordifferent;

or a radical of the formula ##STR22## in which R₈ is as defined above,either R₁₆ and R₁₇, which may be the same or different, each signifieshydrogen; halogen; C₁₋₄ alkyl or C₁₋₄ alkoxy, unsubstituted orsubstituted by phenyl, hydroxy, --CONH₂, cycloalkyl of 5 or 6 carbonatoms, cyano or halogen; phenoxy; or a radical of the formula --CO--Ro,##STR23## --NH--SO₂ --Ro, --CO--NH--Ro, --CON(Ro)₂, --NH--CO--Ro, --SO₂--Ro, --SO₂ --NH--Ro or --SO₂ --N(Ro)₂ ; in which Ro is as definedabove,

or R₁₆ and R₁₇ are on adjacent carbon atoms and are linked to form a--CH═CH--CH═CH-- linkage;

R'₃ signifies hydrogen; or a C₁₋₄ alkyl radical, unsubstituted orsubstituted by phenyl, halogen, C₁₋₄ alkoxy, phenoxy, C₁₋₄alkylcarbonyloxy, phenylcarbonyloxy, cyano orN,N-di(C₁₋₄)alkylcarbamoyl,

either B signifies a 1,4-phenylene radical, and

R'₇ is in a position of said radical ortho to the --N═N-- group andsignifies hydrogen; halogen; C₁₋₄ alkyl or C₁₋₄ alkoxy,

or B signifies a naphthylene radical, preferably a 1,4-naphthyleneradical, and

R'₇ signifies hydrogen;

R'₁ and R'₂ which may be the same or different, each signifies hydrogen,phenyl, or C₁₋₄ alkyl,

Q' signifies an unsubstituted naphthyl radical, an unsubstituted phenylradical, or a phenyl radical substituted by up to 5 halogen atoms or upto two substituents selecting from nitro; halogen; hydroxy; cyano;trihalomethyl; trifluoromethyl; alkyl or alkoxy of 1 to 4 carbon atoms,unsubstituted or substituted by phenyl or phenoxy; phenylazo;cyclohexyl; benzoyloxy; phenylcarbamoyloxy; a group --CORo, ##STR24##--SO₂ --Ro, --SO₂ --NH--Ro, --SO₂ --N(Ro)₂, --CO--NH--Ro, --CO--N(Ro)₂,O--CO--N(Ro)₂ or --NH--CO--Ro, in which Ro is as defined above;##STR25## in which X is as defined above, x signifies 1, 2 or 3,preferably 1;

A.sup.⊖ is as defined above, preferably a halide ZnCl₃.sup.⊖methylsulfate ion or acetate ion.

As will be appreciated, formulae (b) and (c), above, are isomeric formsof formula (a). For convenience, only one formula will be givenhereinafter, it being understood to embrace the isomers. Mixtures of theisomers are obtained when producing the compounds.

In the compounds of formula I', P preferably signifies a radical (a) oran isomer (b) or (c) thereof, a radical (d) or a radical (g). Mostpreferably P signifies a radical (a) or an isomer (b) or (c) thereof.

In radical (a), or isomer (b) or (c) thereof, R₈ preferably signifies analkyl radical of 1 to 4, more preferably 1 or 2, carbon atoms,unsubstituted or substituted by phenyl, e.g. a benzyl radical, hydroxy,e.g. 2-hydroxyethyl and 2-hydroxypropyl, or the group --CONH₂, e.g.2-carboxyamidoethyl (2-carbamoylethyl). R₈ most preferably signifies amethyl radical. R₉ preferably signifies an unsubstituted C₁₋₄, morepreferably C₁₋₂, alkyl radical, or a C₁₋₄, more preferably C₁₋₂, alkylradical substituted by phenyl, e.g. benzyl and phenylethyl, hydroxy,e.g. 2-hydroxyethyl and 2-hydroxypropyl, or the group --CONH₂, e.g.2-carbamoylethyl. Most preferably R₉ signifies a methyl radical. R₁₀preferably signifies a hydrogen atom, a phenyl radical, a cyclohexylradical, an unsubstituted C₁₋₄, more preferably C₁₋₂, alkyl radical, ora C₁₋₄ alkyl, more preferably C₁₋₂, alkyl radical substituted by phenyl,e.g. a benzyl radical. R₁₀ most preferably signifies a hydrogen atom.

Where P signifies a radical (a), or an isomer (b) or (c) thereof, R'₃preferably signifies an alkyl radical of 1 to 4 carbon atoms,unsubstituted or substituted by phenoxy, e.g. 2-phenoxyethyl, phenyl,e.g. benzyl, C₁₋₄ alkoxycarbonyl, e.g. 2-ethoxy carbonylethyl, orphenylcarbonyloxy, e.g. 2-phenylcarbonyloxyethyl. R'₃ more preferablysignifies an unsubstituted C₁₋₄ alkyl, particularly a methyl or ethyl,radical. Most preferably, R'₃ signifies an ethyl radical. R'₂ preferablysignifies a hydrogen atom. R'₁ preferably signifies a hydrogen atom, ora C₁₋₄ alkyl radical, e.g. a methyl radical. R'₁ most preferablysignifies a hydrogen atom or a methyl radical, particularly a hydrogenatom. B preferably signifies a phenylene radical. R'₇ preferablysignifies a hydrogen atom, a C₁₋₄ alkyl radical or a C₁₋₄ alkoxyradical. More preferably R₇ signifies a hydrogen atom or a methylradical and, most preferably, signifies a hydrogen atom. Q' preferablysignifies an unsubstituted naphthyl radical, preferably a 2-naphthylradical, an unsubstituted phenyl radical or a phenyl radical substitutedby up to 5 halogen atoms, preferably chlorine atoms, or by up to twosubstituents, which may be the same or different, selected from halogen,e.g. chlorine, nitro, cyano, phenylsulfonyl, --SO₂ NH(C₁₋₄ alk),preferably --SO₂ NHCH₃, --SO₂ N(C₁₋₄ alk)₂, preferably --SO₂ N(CH₃)₂,##STR26## preferably ##STR27## O--Co--N(C₁₋₄ alkyl)₂, preferably##STR28## C₁₋₄ alkoxy, preferably methoxy, phenoxy, phenylcarbonyloxy,phenylazo, phenylcarbonylamino, phenylaminocarbonyloxy, ##STR29##preferably N,N-dimethylaminocarbonyloxy, N(C₁₋₄alk)-N-phenylaminocarbonyloxy, preferablyN-methyl-N-phenylaminocarbonyloxy, C₁₋₄ alkylsulphonyl, preferablymethylsulphonyl, di-(C₁₋₄)alkylaminosulphonyloxy, preferablydimethylaminosulphonyloxy, trifluoromethyl, unsubstituted C₁₋₄ alkyl,preferably methyl, or C₁₋₄ alkyl substituted by phenyl, preferablybenzyl. Where Q signifies a phenyl radical substituted by up to two suchsubstituents it is generally only monosubstituted. Where Q ismonosubstituted, the substituent is preferably in the para-position. Themost preferred significances of Q' are 2-naphthyl, unsubstituted phenyland phenyl substituted by up to 5 halogen atoms, preferably chlorineatoms. A.sup.⊖ preferably signifies a Cl.sup.⊖, ZnCl₃.sup.⊖, CH₃SO₄.sup.⊖, or acetate ion. x preferably signifies 1.

Where P signifies a radical of formula (d), R₁₁ preferably signifies analkyl radical of 1 to 4, preferably 1 or 2, carbon atoms or an alkoxyradical of 1 to 4 carbon atoms, preferably a methoxy radical. R₁₁ mostpreferably signifies a methyl radical. R₁₂ preferably signifieshydrogen, a C₁₋₄ alkyl radical, preferably a methyl radical, C₁₋₄ alkoxyradical, preferably a methoxy radical, or a halogen atom, preferablychlorine. R₁₂ most preferably signifies hydrogen. q preferablysignifies 1. R'₃ preferably has a significance as given above, when Psignifies (a), more preferably an alkyl radical or 1 to 4 carbon atoms,most preferably a methyl or ethyl radical. R'₂ preferably signifies ahydrogen atom. R'₁ preferably has a significance as given above, when Psignifies (a), more preferably methyl or hydrogen, and most preferably ahydrogen atom. B preferably signifies a phenylene radical. R'₇preferably has a significance as given above, when P signifies (a), morepreferably a hydrogen atom or an alkyl radical of 1 to 4 carbon atoms,e.g. methyl, most preferably hydrogen. Q' preferably has a significanceas given above, where P signifies (a), more preferably an unsubstituted2-naphthyl or phenyl radical, or a phenyl radical substituted by up to 5halogen, preferably chlorine, atoms. A.sup.⊖ preferably signifiesCl.sup.⊖, ZnCl₃.sup.⊖, CH₃.sup.⊖ SO₄ or an acetate ion, and x preferablysignifies 1.

Where P signifies a radical of formula (g), R₈ preferably signifies analkyl radical of 1 to 4, preferably 1 or 2, carbon atoms, unsubstitutedor substituted by -CONH₂, e.g. 2-carbamoylethyl. R₈ more preferablysignifies a methyl or ethyl radical, most preferably a methyl radical.R₁₆ and R₁₇, which may be the same or different, each preferably signifyhydrogen; chlorine, C₁₋₄ alkoxy, preferably methoxy, unsubstituted orsubstituted by phenyl, e.g. benzyloxy; C₁₋₄ alkylcarbonyl, preferablymethylcarbonyl; C₁₋₄ alkylaminocarbonyl, preferably methylaminocarbonyl;phenylcarbonylamino; C₁₋₄ alkylsulphonylamino, preferablymethylsulphonylamino; phenoxy; di-C₁₋₄ (di-C₁₋₄ alkylsulfamoyl),preferably dimethylaminosulphonyl; or phenylsulphonyl, or R₁₆ and R₁₇are on adjacent carbon atoms and form a --CH═CH--CH═CH-- linkage. Mostpreferably one of R₁₆ and R₁₇ signifies hydrogen, the other methoxy. R₃' preferably has one of the significances given above, when P signifies(a), more preferably a methyl or ethyl radical. R₂ ' preferablysignifies a hydrogen atom. R₁ ' preferably has a significance givenabove when P signifies (a), more preferably methyl or hydrogen. Bpreferably signifies a phenylene radical. R₇ preferably has asignificance given above, when P signifies (a), more preferably methylor hydrogen, most preferably hydrogen. Q' preferably has a significancegiven above, where P signifies (a), most preferably an unsubstituted2-naphthyl radical, an unsubstituted phenyl radical or a phenyl radicalsubstituted by up to 5 halogen, preferably chlorine, atoms. X preferablysignifies 1 and A.sup.⊖ preferably signifies Cl.sup.⊖, ZnCl₃.sup.⊖, CH₃SO₄.sup.⊖ or an acetate ion.

Thus, the preferred compounds of Formula I' when P is a group of Formula(g) are those where

R₈ is C₁₋₄ alkyl or C₁₋₄ alkyl substituted by carbamoyl, and

each of R₁₆ and R₁₇ is independently hydrogen; C₁₋₄ alkoxy; C₁₋₄ alkoxysubstituted by phenyl; C₁₋₄ alkylcarbonyl; C₁₋₄ alkylcarbamoyl;benzamido; C₁₋₄ alkylsulfonylamino; phenoxy or phenylsulfonyl or

R₁₆ and R₁₇ taken together are --CH═CH--CH═CH--,

especially those of this group wherein

R₁ ' is hydrogen or methyl,

R₂ ' is hydrogen,

R₃ ' is methyl or ethyl,

R₇ ' is hydrogen or methyl,

B is 1,4-phenylene,

Q is phenyl, naphthyl or phenyl substituted by 1 to 5 chlorosubstituents, and

x is 1.

Representative compounds of formula I' are those in which x signifies 1,R₂ ' signifies hydrogen, R₁ ' signifies a hydrogen atom or an alkylradical of 1 to 4 carbon atoms, and P signifies a radical of the formula##STR30## in which R₈ ' and R₉ ', which may be the same or different,each signifies an alkyl radical of 1 to 4 carbon atoms, unsubstituted orsubstituted by phenyl, hydroxy or --CONH₂ ;

R₁₀ ' signifies a hydrogen atom, an alkyl radical of 1 to 4 carbonatoms, a phenyl (C₁₋₄)alkyl radical or a phenyl radical;

a radical of the formula ##STR31## in which R₁₁ ' signifies C₁₋₄ alkyl;

R₁₂ ' signifies hydrogen; halogen; C₁₋₄ alkyl or C₁₋₄ alkoxy;

a radical of the formula ##STR32## in which R₁₃ ' signifies hydrogen oran alkyl radical of 1 to 4 carbon atoms,

R₁ ' is as defined above, and

R₁₄ ' signifies hydrogen;

a radical of the formula ##STR33## in which R₈ ', R₁₄ ' and R₉ ' are asdefined above, or a radical of the formula ##STR34## in which either R₁₆' and R₁₇ ', which may be the same or different, each signifieshydrogen; C₁₋₄ alkyl or C₁₋₄ alkoxy, unsubstituted or substituted byphenyl or phenoxy;

or R₁₆ ' and R₁₇ ' are on adjacent carbon atoms and are linked to form a--CH═CH--CH═CH-- linkage; and

R₈ ' is as defined above.

Still further preferred compounds of formula I are the compounds of theformula I", ##STR35## in which P' signifies a radical of formula##STR36## or an isomer thereof, ##STR37##

R₅₃ signifies a hydrogen atom, a methyl radical, a phenyl radical or abenzyl radical.

R₅₄ and R₅₅, independently, signify an unsubstituted alkyl radical of 1to 4 carbon atoms, preferably a methyl or ethyl radical, or an alkylradical of 1 to 4 carbon atoms substituted by a hydroxy radical or thegroup --CONH₂,

R₅₇ signifies a hydrogen atom or an alkoxy radical of 1 to 4 carbonatoms, preferably a methoxy radical,

R₅₉ signifies an alkyl radical of 1 to 4 carbon atoms, preferably amethyl or ethyl radical, unsubstituted or substituted by the group--CONH₂,

R₆₀ signifies an alkyl or alkoxy radical of 1 to 4 carbon atoms,preferably a methyl or ethyl radical,

R₆₂ signifies an alkyl radical of 1 to 4 carbon atoms, preferably amethyl radical,

R₆₃ signifies a hydrogen atom or a group (C₁₋₄ alk)₂ NSO₂ --, preferably(CH₃)₂ NSO₂ --,

R₆₄ signifies an alkyl radical of 1 to 4 carbon atoms, preferably amethyl radical,

R₆₅ and R₆₆, which may be the same or different, each signify an alkylradical of 1 to 4 carbon atoms, preferably a methyl radical,

B signifies a 1,4-phenylene radical, unsubstituted or substituted in theortho position to the azo group by alkyl of 1 to 4 carbon atoms,preferably methyl,

R₅₀ signifies an alkyl radical of 1 to 4 carbon atoms, unsubstituted orsubstituted by phenyl,

R₅₁ signifies a hydrogen atom or an alkyl radical of 1 to 4 carbonatoms, preferably a methyl radical,

Q" signifies an unsubstituted naphthyl, preferably a 2-naphthyl,radical, an unsubstituted phenyl radical, a phenyl radical substitutedby up to two substituents, preferably one substituent, selected fromhydroxy, halogen, preferably chlorine, C₁₋₄ alkoxycarbonyl, preferablymethoxycarbonyl, phenoxy, phenylcarbonyl, cyclohexyl, alkyl of 1 to 4carbon atoms, preferably methyl, unsubstituted or substituted by up tothree halogen atoms or by a phenyl radical; or Q" signifies a phenylradical substituted by up to 5 halogen atoms, preferably chlorine atoms,and A.sup.⊖ is as defined above, preferably chloride, ZnCl₃.sup.⊖,methylsulfate or acetate.

In the compounds of formula I", P' preferably signifies a radical offormula (a"), (b") or (c"), most preferably a radical of (a").

Representative of the compounds of formula I" are the compounds offormula Ia", ##STR38## in which R₅₄ and R₅₅ are as defined above,

R_(50a) signifies an unsubstituted alkyl radical of 1 to 4 carbon atoms,preferably a methyl, ethyl or butyl radical;

R_(51a) signifies hydrogen or a methyl radical,

Q_(a) " signifies an unsubstituted naphthyl radical, an unsubstitutedphenyl radical, a phenyl radical substituted by up to two methylradicals, a phenyl radical substituted by up to five halogen atoms,preferably chlorine atoms; or a 3-hydroxy-4-phenylcarbonylphenylradical, and

A.sup.⊖ is as defined above, preferably a ZnCl₃.sup.⊖, Cl.sup.⊖, CH₃SO₄.sup.⊖ or acetate ion.

As examples of alkyl and alkoxy radicals of 1 to 4 carbon atoms may begiven methyl, ethyl, n-propyl, isopropyl and n-butyl and thecorresponding alkoxy radicals. Unless otherwise stated, the preferredsuch radicals are methyl, ethyl, methoxy and ethoxy, methyl and methoxybeing most preferred. By the term halogen, as used herein, is meantchlorine, bromine and iodine; chlorine and bromine being preferred,chlorine being most preferred.

The compounds of formula I are useful as dyes. They may be convertedinto dyeing preparations, e.g. into stable, liquid or solid dyeingpreparations, in conventional manner, e.g. by grinding or granulating ordissolving in conventional dyestuff solvents, if necessary with theaddition of assistants such as stabilizers. Such preparations may beproduced, for example, in accordance with French Pat. Nos. 1,572,030 and1,581,900.

The compounds of formula I may be used in the dyeing and printing oftextile substrates, whether in fibre, yarn or fibric form, which consistof or comprise homopolymers or co-polymers of acrylonitrile orasymmetrical dicyanoethylene. The dyeing of such substrates may becarried out in conventional manner.

The compounds of formula I may also be used for dyeing or printingsubstrates of synthetic polyamide or synthetic polyester fibres,modified by the introduction of acid groups. Polyamides of this type aredescribed in Belgian Pat. No. 706,104 and polyester fibres of this typeare described in U.S. Pat. No. 3,379,723. The dyeing of such substratesmay be carried out in conventional manner. It is advantageous to dye inan aqueous, neutral or acid medium, at from 60° C. to the boil or attemperatures above 100° C. under pressure.

The dyeings obtained with the compounds of formula I are level, havestable light fastness as well as good wet fastness properties, e.g. towashing, perspiration, sublimation, pleating, decatizing, pressing,steam, water, sea water, dry cleaning, crossdyeing and solvents. Thedyes are well soluble in water, show good compatibility with salt, goodstability to boiling, good pH stability and partly reserve fibres otherthan those on which they are dyeable. Further, they possess good powerof build-up in combination with other basic dyes.

The compounds, which have good solubility in organic solvents, may alsobe used for the dyeing of natural or synthetic resins in the mass, beingincorporated therein in conventional manner, e.g. by intimate admixturetherein, for example by milling, optionally with the use of a solvent.

It has been found that mixtures of two or more of the compounds of thepresent invention or of one of the compounds of the present inventionamd other cationic dyes can be used with advantage.

The following Examples, in which parts and percentages are by weight andtemperatures are in degrees centigrade, illustrate the invention.

EXAMPLE 1

8.4 Parts of 3-amino-1,2,4-triazole are dissolved in 22 parts of 62%nitric acid and 18 parts water. The solution is mixed with 20 parts iceand over a period of 20 minutes, 20.8 parts 4 N sodium nitrite solutionis added dropwise. After 30 minutes the excess nitrite is decomposedwith 0.4 parts aminosulphonic acid and the diazo solution is, over aperiod of 20 minutes, dropped into a solution consisting of 24.1 partsN-ethyl-N-2'-phenoxyethylaniline (prepared according to known methods),25 parts glacial acetic acid and 10 parts ice. The pH is adjusted to3.5-4.0 by the addition of a concentrated caustic soda solution, thedyestuff suspension is stirred and filtered to obtain the dye product.The vacuum dried dye is suspended in 150 parts benzene and 35 partscyclohexane, filtered and washed with 100 parts cyclohexane.

26.8 Parts of the dried and finely ground dye is suspended in 80 partswater, 3.5 parts magnesium oxide and 18 parts dimethylsulphate andheated to 45° to 50° for 30 minutes. After cooling to room temperature,the solution is diluted with 800 parts water, mixed with 2.5 parts"Norit Supra" and filtered using a talc filter. The dye is salted outfrom the filtrate with 10.2 parts zinc chloride and 80 parts sodiumchloride, washed with 100 parts of a 10% aqueous solution of sodiumchloride and dried at 50° under vacuum.

34.8 Parts of the dye of the formula ##STR39## are obtained which onpolyacrylonitrile and acid-modified polyester fibres gives bluish-reddyeings.

Application Example A

20 Parts of the dye of Example 1 and 80 parts dextrin are ground for 4hours in a powder mill. 1 Part of the preparation so obtained is madeinto a paste with 1 part 40% acetic acid, then 200 parts demineralizedwater are poured onto the paste and the mixture is boiled for a shorttime. (The same dye and dextrin mixture can also be formed into a pastewith 100 parts water and finally be spray dried.) The mixture is thendiluted with 7000 parts demineralized water, mixed with 2 parts glacialacetic acid and is put into a bath at 60° with 100 partspolyacrylonitrile fabric. The fabric may be pretreated for 10 to 15minutes at 60° in a bath consisting of 8000 parts water and 2 partsglacial acetic acid.

The dyebath is raised to 98° to 100° over a period of 30 minutes, boiledfor 11/2 hours and the fabric is rinsed. A bluish-red dyeing with goodlight and wet fastness properties is obtained.

10 Parts of the dye of Example 1 are dissolved in 60 parts glacialacetic acid and 30 parts water. A stable concentrated solution, with adye content of about 10%, is obtained, which solution can be used to dyepolyacrylonitrile according to the above-mentioned process.

Application Example B

20 Parts of the dye of Example 1 are mixed with 80 parts dextrin in aball-mill for 48 hours; 1 part of the preparation so obtained is madeinto a paste with 1 part 40% acetic acid; 200 parts demineralized waterare poured onto the paste and the mixture is boiled for a short time.With this solution the following dyeings are made:

(a) The solution is diluted with 7000 parts of demineralized water andmixed with 21 parts of anhydrous sodium sulphate, 14 parts of ammoniumsulphate, 14 parts of formic acid and 15 parts of a carrier based on thereaction product of ethylene oxide with dichlorophenolene are put into abath at 60° with 100 parts of a polyester fabric, which fabric has beenmodified with acid groups. The fabric may be pretreated for 10 to 15minutes at 60° in a bath consisting of 8000 parts of water and 2 partsof glacial acetic acid.

The dyebath is raised to 98°-100° over a period of 30 minutes, boiledfor 11/2 hours and the fabric rinsed. A similar bluish-red dyeing withgood wet fastness is obtained.

(b) The solution is diluted with 3000 parts of demineralized water andmixed with 18 parts of anhydrous sodium sulphate, together with 6 partsof ammonium sulphate and formic acid and put into the bath at 60° with100 parts of a polyester fabric, which fabric has been modified withacid groups. The closed vessel is heated to 110° over a period of 45minutes, kept at this temperature for one hour with shaking, cooled to60° within 25 minutes and the dyed fabric rinsed. A similar bluish-reddyeing with good wet fastness is obtained.

(c) The same procedure as described in paragraph (b) above is carriedout except that the closed vessel is heated for one hour at 120°.

The structural composition of further dyes is shown in the followingTable I, which dyes can be produced in accordance with the procedure ofExample 1 and agree with the formula ##STR40## in which R, R₁ and R₄ toR₉ have the significances as shown in the columns of Table I.

The anion A.sup.⊖ may be any one of those named in the foregoingdescription. A further column indicates the shade of dyeing onpolyacrylonitrile.

                                      TABLE I                                     __________________________________________________________________________                                                          Dye-shade on                                                                  poly-                   Ex.                                                                              R       R.sub.1                                                                            R.sub.4                                                                         R.sub.5 R.sub.6                                                                            R.sub.7    R.sub.8   R.sub.9                                                                         acrylonitrile           __________________________________________________________________________    2  H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          H         Cl                                                                              bluish-red              3  H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          Cl        Cl                                                                              "                       4  H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          CH.sub.3  H "                       5  H       CH.sub.3                                                                           H CH.sub.3                                                                              CH.sub.3                                                                           C.sub.2 H.sub.5                                                                          H         H "                       6  H       CH.sub.3                                                                           H CH.sub.3                                                                              CH.sub.3                                                                           C.sub.2 H.sub.5                                                                          Cl        H "                       7  H       CH.sub.3                                                                           H CH.sub.3                                                                              CH.sub.3                                                                           C.sub.2 H.sub.5                                                                          CH.sub.3  H "                       8  H       CH.sub.3                                                                           H CH.sub.3                                                                              OCH.sub.3                                                                          C.sub.2 H.sub.5                                                                          H         H "                       9  H       CH.sub.3                                                                           H CH.sub.3                                                                              H    CH.sub.3   H         H "                       10 H       CH.sub.3                                                                           H CH.sub.3                                                                              H                                                                                   ##STR41## H         H red                     11 H       CH.sub.3                                                                           H CH.sub.3                                                                              H                                                                                   ##STR42## H         H red                     12 H       CH.sub.3                                                                           H CH.sub.3                                                                              H                                                                                   ##STR43## H         H scarlet                 13 H       CH.sub.3                                                                           H CH.sub.3                                                                              H                                                                                   ##STR44## H         H red                     14 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.4 H.sub.9                                                                          H         H bluish-red              15 H       C.sub.2 H.sub.5                                                                    H C.sub.2 H.sub.5                                                                       H    C.sub.2 H.sub.5                                                                          H         H "                       16 H       CH.sub.3                                                                           H                                                                                ##STR45##                                                                            H    C.sub.2 H.sub.5                                                                          H         H "                       17 H       CH.sub.3                                                                           H C.sub.2 H.sub.5                                                                       H    C.sub.2 H.sub. 5                                                                         H         H "                       18 H       CH.sub.3                                                                           H                                                                                ##STR46##                                                                            H    C.sub.2 H.sub.5                                                                          H         H strong bluish red       19 H       CH.sub.3                                                                           H                                                                                ##STR47##                                                                            H    C.sub.2 H.sub.5                                                                          H         H bluish-red              20 CH.sub.3                                                                              CH.sub.3                                                                           H CH.sub.3                                                                              H    CH.sub.3   H         H "                       21 CH.sub.3                                                                              CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          H         H "                       22 CH.sub.3                                                                              CH.sub.3                                                                           H CH.sub.3                                                                              H                                                                                   ##STR48## H         H "                       23 CH.sub.3                                                                              CH.sub.3                                                                           H CH.sub.3                                                                              CH.sub.3                                                                           C.sub.2 H.sub.5                                                                          H         H "                       24                                                                                ##STR49##                                                                            CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          H         H "                       25                                                                                ##STR50##                                                                            CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub. 2 H.sub.5                                                                         Cl        H "                       26                                                                                ##STR51##                                                                            CH.sub.3                                                                           H CH.sub.3                                                                              H    CH.sub.3   H         H "                       27                                                                                ##STR52##                                                                            CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.4 H.sub.9                                                                          H         H "                       28                                                                                ##STR53##                                                                            CH.sub.3                                                                           H CH.sub.3                                                                              CH.sub.3                                                                           C.sub.2 H.sub.5                                                                          H         H "                       29                                                                                ##STR54##                                                                            C.sub.2 H.sub.5                                                                    H C.sub.2 H.sub.5                                                                       H    C.sub.2 H.sub.5                                                                          H         H "                       30                                                                                ##STR55##                                                                            CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          H         H strong bluish-red       31                                                                                ##STR56##                                                                            CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          Cl        H "                       32                                                                                ##STR57##                                                                            CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          Cl        Cl                                                                              "                       33                                                                                ##STR58##                                                                            CH.sub.3                                                                           H CH.sub.3                                                                              H    CH.sub.3   H         H "                       34                                                                                ##STR59##                                                                            CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.4 H.sub.9                                                                          H         H "                       35                                                                                ##STR60##                                                                            C.sub.2 H.sub.5                                                                    H C.sub.2 H.sub.5                                                                       H    C.sub.2 H.sub.5                                                                          H         H "                       36                                                                                ##STR61##                                                                            CH.sub.3                                                                           H CH.sub.3                                                                              CH.sub.3                                                                           C.sub.2 H.sub.5                                                                          H         H "                       37                                                                                ##STR62##                                                                            CH.sub.3                                                                           H                                                                                ##STR63##                                                                            H    C.sub.2 H.sub.5                                                                          H         H reddish-violet          38 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          NO.sub.2  H bluish-red              39 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          CN        H "                       40 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                           ##STR64##                                                                              H "                       41 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          SO.sub.2 NHCH.sub.3                                                                     H "                       42 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          SO.sub.2N(CH.sub.3).sub.2                                                               H "                       __________________________________________________________________________                                                          Dye-shade on                                                                  poly-                   Ex.                                                                              R       R.sub.1                                                                            R.sub.4                                                                         R.sub.5 R.sub.6                                                                            R.sub.7    R.sub.8     acrylonitrile           __________________________________________________________________________    43 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          CF.sub.3    bluish-red              44 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          COOCH.sub.3 "                       45 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          CONHCH.sub.3                                                                              "                       46 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          OCH.sub.3   "                       47 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                           ##STR65##  "                       48 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                           ##STR66##  "                       49 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                           ##STR67##  "                       50 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                           ##STR68##  "                       51 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                           ##STR69##  "                       52 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                           ##STR70##  "                       53 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                           ##STR71##  "                       54 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                           ##STR72##  "                       __________________________________________________________________________                                                          Dye-shade on                                                                  poly-                   Ex.                                                                              R       R.sub.1                                                                            R.sub.4                                                                         R.sub.5 R.sub.6                                                                            R.sub.7    R.sub.8   R.sub.9                                                                         acrylonitrile           __________________________________________________________________________    55 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          SO.sub.2CH.sub.3                                                                        H bluish-red              56 H        CH.sub.3                                                                          H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                          OSO.sub.2N(CH.sub.3).sub.2                                                              H "                       57 H       CH.sub.3                                                                           H CH.sub.3                                                                              H    C.sub.2 H.sub.5                                                                           ##STR73##                                                                              H "                       __________________________________________________________________________

    __________________________________________________________________________    Ex.                               Dye shade on poly-                                                            acrylonitrile                               __________________________________________________________________________        ##STR74##                     bluish-red                                      ##STR75##                     bluish-red                                  60.                                                                               ##STR76##                     bluish-red                                      ##STR77##                     bluish-red                                      ##STR78##                     bluish-red                                      ##STR79##                     bluish-red                                  __________________________________________________________________________

EXAMPLES 64 AND 65

8.4 Parts 3-amino-1,2,4-triazole are dissolved in 22 parts 62% nitricacid and 18 parts water. The solution is mixed with 20 parts ice and isadded dropwise, over a period of 20 minutes, to an aqueous solution of 4N sodium nitrite. After 30 minutes the excess nitrite is decomposed with0.4 parts aminosulphonic acid and the diazo solution, over a period of20 minutes, is added dropwise to a solution containing 29.1 parts of thecoupling component of the formula ##STR80##

25 parts glacial acetic acid and 10 parts ice. The pH is adjusted to 4.0to 4.5 with sodium hydroxide, the suspension is stirred for 15 hours andfiltered to obtain the dye product. The dried dye is suspended in 100parts benzene and 100 parts cyclohexane, stirred for 1 hour at 40° andfiltered at room temperature.

31.8 Parts of the dried and ground dye are dissolved in 250 partschloroform at 50° and are mixed with 6.5 parts magnesium oxide. Over aperiod of 10 minutes, 25 parts dimethyl sulphate are added dropwise andthe mixture is stirred for 2 hours at 50° to 60°. After cooling to roomtemperature, the suspension is diluted with 250 parts chloroform andfiltered onto "Hyflo". The chloroform phase is extracted three timeswith a total of 2000 parts of a 5% aqueous sodium chloride solution. Thesolvent is extracted under vacuum and the residue is dried overGlauber's salt. After dissolving the dye residue in 1000 parts water at70° to 80°, 10 parts zinc chloride and 50 parts sodium chloride areadded and after 20 hours of stirring the resulting dye is obtained byfiltration.

After drying at 50° under vacuum, 31.2 parts of the dye of the formula##STR81## is obtained which gives a fast red shade on polyester fibres.

Using the coupling component of the formula ##STR82## instead of theabove-mentioned coupling component and employing the same procedure, thedye of the formula ##STR83## is obtained which when used in an aciddyebath gives the same red colour on polyacrylonitrile and acid-modifiedpolyester fibres.

The coupling components used above may be prepared with good yields andpurity by condensing N-ethyl-N-2'-chloroethylaniline with β-naphthol orα-naphthol at 110° to 120° without a solvent in the presence of a base,such as sodium hydroxide, and with a catalytic amount of calcium iodide.

The structural composition of further dyes is shown in the followingTable II. They may be prepared in accordance with the procedure ofExamples 64 and 65 and correspond with the formula ##STR84## in which R₁to R₆ and Z have the significances as shown in the columns of the Table.A further column indicates the dye shade on polyacrylonitrile.

The anion A.sup.⊖ may be any one of those named in the foregoingdescription.

                                      TABLE II                                    __________________________________________________________________________                                                          Dye-shade on            Ex.                                                                              R.sub.1 R.sub.2   R.sub.3   R.sub.4                                                                            R.sub.5                                                                            R.sub.6                                                                            Z       polyacrylonitrile       __________________________________________________________________________    66 H       CH.sub.3  CH.sub.3  H    H    CH.sub.3                                                                            ##STR85##                                                                            bluish-red              67 H       CH.sub.3  CH.sub.3  H    H    CH.sub.3                                                                            ##STR86##                                                                            "                       68 H       CH.sub.3  CH.sub.3  H    CH.sub.3                                                                           CH.sub.3                                                                            ##STR87##                                                                            "                       69 H       CH.sub.3  CH.sub.3  H    CH.sub.3                                                                           CH.sub.3                                                                            ##STR88##                                                                            "                       70 H       CH.sub.3  CH.sub.3  CH.sub.3                                                                           H    C.sub.2 H.sub.5                                                                     ##STR89##                                                                            "                       71 H       CH.sub.3  CH.sub. 3 CH.sub.3                                                                           H    C.sub.2 H.sub.5                                                                     ##STR90##                                                                            "                       72 H       CH.sub.3  CH.sub.3  CH.sub.3                                                                           CH.sub.3                                                                           C.sub.2 H.sub.5                                                                     ##STR91##                                                                            "                       73 H       CH.sub.3  CH.sub.3  CH.sub.3                                                                           CH.sub.3                                                                           C.sub.2 H.sub.5                                                                     ##STR92##                                                                            "                       74 H       CH.sub.3  CH.sub.3  H    H    C.sub.4 H.sub.9                                                                     ##STR93##                                                                            bluish-red              75 H       CH.sub.3  CH.sub.3  Cl   H    C.sub.2 H.sub.5                                                                     ##STR94##                                                                            scarlet                 76 H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         H    H    C.sub.2 H.sub.5                                                                     ##STR95##                                                                            bluish-red              77 H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         H    H    C.sub.2 H.sub.5                                                                     ##STR96##                                                                            "                       78 H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         H    CH.sub.3                                                                           CH.sub.3                                                                            ##STR97##                                                                            "                       79 H       C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         H    CH.sub.3                                                                           CH.sub.3                                                                            ##STR98##                                                                            "                       80 H       CH.sub.3                                                                                 ##STR99##                                                                              H    H    C.sub.2 H.sub.5                                                                     ##STR100##                                                                           red                     81 H       CH.sub.3                                                                                 ##STR101##                                                                             H    H    C.sub.2 H.sub.5                                                                     ##STR102##                                                                           red                     82 CH.sub.3                                                                              CH.sub.3  CH.sub.3  H    H    C.sub.2 H.sub.5                                                                     ##STR103##                                                                           bluish-red              83 CH.sub.3                                                                              CH.sub.3  CH.sub.3  H    H    C.sub.2 H.sub.5                                                                     ##STR104##                                                                           bluish-red              84                                                                                ##STR105##                                                                           CH.sub.3  CH.sub.3  H    H    C.sub.2 H.sub.5                                                                     ##STR106##                                                                           strong bluish- red      85                                                                                ##STR107##                                                                           CH.sub.3  CH.sub.3  H    H    C.sub.2 H.sub.5                                                                     ##STR108##                                                                           strong bluish- red      86                                                                                ##STR109##                                                                           CH.sub.3  CH.sub.3  H    CH.sub.3                                                                           C.sub.2 H.sub.5                                                                     ##STR110##                                                                           strong bluish- red      87                                                                                ##STR111##                                                                           CH.sub.3  CH.sub.3  H    CH.sub.3                                                                           C.sub.2 H.sub.5                                                                     ##STR112##                                                                           strong bluish- red      88                                                                                ##STR113##                                                                           CH.sub.3  CH.sub.3  CH.sub.3                                                                           H    C.sub.2 H.sub.5                                                                     ##STR114##                                                                           strong bluish- red      89                                                                                ##STR115##                                                                            CH.sub.3 CH.sub.3  CH.sub.3                                                                           H    C.sub.2 H.sub.5                                                                     ##STR116##                                                                           strong bluish- red      90                                                                                ##STR117##                                                                            ##STR118##                                                                             CH.sub.3  H    H    C.sub.2 H.sub.5                                                                     ##STR119##                                                                           strong bluish- red      91                                                                                ##STR120##                                                                            ##STR121##                                                                             CH.sub.3  H    H    C.sub.2 H.sub.5                                                                     ##STR122##                                                                           strong bluish- red      92 H                                                                                      ##STR123##                                                                             CH.sub.3  H    H    C.sub.2 H.sub.5                                                                     ##STR124##                                                                           bluish-red              93 H       CH.sub.2 CH.sub.2 OH                                                                    C.sub.2 H.sub.4 OH                                                                      H    H    C.sub.2 H.sub.5                                                                     ##STR125##                                                                           "                       94 H       CH.sub.2 CH.sub.2 OH                                                                    C.sub.2 H.sub.4 OH                                                                      H    H    C.sub. 2 H.sub.5                                                                    ##STR126##                                                                           "                       95 H                                                                                      ##STR127##                                                                              ##STR128##                                                                             H    H    C.sub.2 H.sub.5                                                                     ##STR129##                                                                           "                       96 H                                                                                      ##STR130##                                                                              ##STR131##                                                                             H    H    C.sub.2 H.sub.5                                                                     ##STR132##                                                                           "                       97 H       C.sub.2 H.sub.4 CONH.sub.2                                                              C.sub.2 H.sub.4 CONH.sub.2                                                              H    H    C.sub.2 H.sub.5                                                                     ##STR133##                                                                           "                       98 H       C.sub.2 H.sub.4 CONH.sub.2                                                              C.sub.2 H.sub.4 CONH.sub.2                                                              H    H    C.sub.2 H.sub.5                                                                     ##STR134##                                                                           "                       99 H       CH.sub.3  CH.sub.3  H                                                                                   ##STR135##                                                                        C.sub.2 H.sub.                                                                      ##STR136##                                                                           "                       100                                                                              H       CH.sub.3  CH.sub.3  H                                                                                   ##STR137##                                                                        C.sub.2 H.sub.5                                                                     ##STR138##                                                                           bluish-red              101                                                                               ##STR139##                                                                           CH.sub.3  CH.sub.3  OCH.sub.3                                                                          H    C.sub.2 H.sub.5                                                                     ##STR140##                                                                           "                       102                                                                               ##STR141##                                                                           CH.sub.3  CH.sub.3  H    H    C.sub.2 H.sub.5                                                                     ##STR142##                                                                           "                       103                                                                               ##STR143##                                                                           CH.sub.3  CH.sub.3  H    H    C.sub.2 H.sub.5                                                                     ##STR144##                                                                           "                       __________________________________________________________________________

EXAMPLE 104

18 Parts 2-amino-6-methoxybenzothiazole are dissolved in 100 partsglacial acetic acid and 90 parts sulphuric acid are added thereto withice cooling so that the temperature does not rise above 35° to 40°.Finally, 100 parts ice are added and, at a temperature between -5° and0°, a solution consisting of 7.3 parts sodium nitrite and 25 parts wateris added dropwise. The mixture is stirred, with cooling, for 1 hour andthereupon it is mixed with a solution containing 24.1 parts of acoupling component of the formula ##STR145## dissolved in 25 partsglacial acetic acid. The reaction mixture is stirred at room temperaturefor 3 hours and then the pH is adjusted to 3 with 170 parts of a 30%aqueous solution of sodium hydroxide and the temperature is kept under35° by cooling. The resulting dye is filtered, washed thoroughly withwater and dried under vacuum at 50°.

21.5 Parts of the dried and ground dye are stirred with 200 partsglacial acetic acid, mixed with 2.2 parts magnesium oxide and themixture is heated to 60° to 70°. Over a period of 15 minutes, 14 partsdimethylsulphate are added dropwise and the mixture is stirred for 3hours at 70° to 75°. The reaction mixture is diluted with 2000 partswater and the dye is salted out with 15 parts zinc chloride and 80 partssodium chloride. It is filtered, washed with 100 parts of a 5% aqueoussolution of sodium chloride and dried at 50° under vacuum 23.8 Parts ofthe dye of the formula ##STR146## are obtained which onpolyacrylonitrile and acid-modified polyester fibres gives fast dyeingsof a pure blue colour.

EXAMPLE 105

Instead of the last-mentioned coupling component, the coupling componentof the formula ##STR147## is used a similar dye of the formula##STR148## is obtained which likewise gives fast dyeings of a blue shadeon polyacrylonitrile and acid-modified polyester fibres.

The structural composition of further dyes is shown in the followingTable III. The dyes can be obtained in accordance with the procedure ofthe foregoing Examples and correspond with the formula ##STR149## inwhich R₂₀ to R₂₅ and Z₁ have the significances as shown in the columnsof the Table. The anion A.sup.⊖ may be any one of those named in theforegoing description.

    __________________________________________________________________________                                                    Dye-shade on                  Ex.                                                                              R.sub.20  R.sub.21                                                                          R.sub.22 R.sub.23                                                                           R.sub.24                                                                          R.sub.25                                                                           Z.sub.1 polyacrylonitrile             __________________________________________________________________________    106                                                                              H         H   CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR150##                                                                           blue                          107                                                                              H         H   CH.sub.3 CH.sub.3                                                                           H   C.sub.2 H.sub.5                                                                     ##STR151##                                                                           "                             108                                                                              H         H   CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR152##                                                                           "                             109                                                                              H         H   CH.sub.3 H    CH.sub.3                                                                          CH.sub.3                                                                            ##STR153##                                                                           "                             110                                                                              CH.sub.3 O                                                                              H   CH.sub.3 H    H   CH.sub.3                                                                            ##STR154##                                                                           "                             111                                                                              CH.sub.3 O                                                                              H   CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR155##                                                                           "                             112                                                                              CH.sub.3 O                                                                              H   CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR156##                                                                           greenish-blue                 113                                                                              CH.sub.3 O                                                                              H   CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR157##                                                                           greenish-blue                 114                                                                              CH.sub.3 O                                                                              H   "        H    H   C.sub.2 H.sub.5                                                                     ##STR158##                                                                           "                             115                                                                              CH.sub.3 O                                                                              H   "        H    H   C.sub.2 H.sub.5                                                                     ##STR159##                                                                           "                             116                                                                              CH.sub.3 O                                                                              H   "        H    H   C.sub.2 H.sub.5                                                                     ##STR160##                                                                           "                             117                                                                              CH.sub.3 O                                                                              H   "        H    H   C.sub.2 H.sub.5                                                                     ##STR161##                                                                           "                             118                                                                              CH.sub.3 O                                                                              H   C.sub.2 H.sub.5 CONH.sub.2                                                             H    H   C.sub.2 H.sub.5                                                                     ##STR162##                                                                           "                             119                                                                              CH.sub.3 O                                                                              H   C.sub.2 H.sub.4 OH                                                                     H    H   C.sub.2 H.sub.5                                                                     ##STR163##                                                                           "                             120                                                                              CH.sub.3O H                                                                                  ##STR164##                                                                            H    H   C.sub.2 H.sub.5                                                                     ##STR165##                                                                           greenish-blue                 121                                                                              "         H   C.sub.2 H.sub.5                                                                        H    H   C.sub.2 H.sub.5                                                                     ##STR166##                                                                           "                             122                                                                              "         H   C.sub.2 H.sub.5                                                                        H    CH.sub.3                                                                          CH.sub.3                                                                            ##STR167##                                                                           "                             123                                                                              "         H   CH.sub.3 CH.sub.3                                                                           H   C.sub.2 H.sub.5                                                                     ##STR168##                                                                           blue                          124                                                                              "         H   CH.sub.3 CH.sub.3                                                                           CH.sub.3                                                                          CH.sub.3                                                                            ##STR169##                                                                           "                             125                                                                              "         H   CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR170##                                                                           greenish-blue                 126                                                                              "         H   CH.sub.3 Cl   H   C.sub.2 H.sub.5                                                                     ##STR171##                                                                           blue                          127                                                                              "         H   CH.sub.3 CH.sub.3 O                                                                         H   C.sub.2 H.sub.5                                                                     ##STR172##                                                                           "                             128                                                                              OCH.sub.2O    CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR173##                                                                           blue                          129                                                                              CH.sub.3  CH.sub.3                                                                          CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR174##                                                                           "                             130                                                                              Cl        H   CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR175##                                                                           greenish-blue                 131                                                                              CH.sub.3  H   CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR176##                                                                           blue                          132                                                                               ##STR177##                                                                             "   CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR178##                                                                           greenish-blue                 133                                                                               ##STR179##                                                                             "   CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR180##                                                                           "                             134                                                                               ##STR181##                                                                             "   CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR182##                                                                           "                             135                                                                               ##STR183##                                                                             "   CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR184##                                                                           "                             136                                                                              CH.sub.3SO.sub.2NH                                                                      H   CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR185##                                                                           greenish-blue                 137                                                                              (CH.sub.3).sub.2 NSO.sub.2                                                              "   CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR186##                                                                           "                             138                                                                              R.sub.20 together with R.sub.21                                                             CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR187##                                                                           "                                 ##STR188##                                                                139                                                                              R.sub.20 together with R.sub.21                                                             CH.sub.3 H    H   CH.sub.3                                                                            ##STR189##                                                                           "                                 ##STR190##                                                                140                                                                               ##STR191##                                                                             H   CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR192##                                                                           "                             141                                                                               ##STR193##                                                                             "   CH.sub.3 H    H   C.sub.2 H.sub.5                                                                     ##STR194##                                                                           "                             __________________________________________________________________________

EXAMPLE 142

By diazotizing 33 parts 2-aminopyridine-N-oxide and coupling with asolution of 87.3 parts N-ethyl-N-2'β-naphthyloxyethylaniline indimethylformamide, (at the same time removing the oxygen atom of theN-oxide group), according to known methods such as, for example, thosedescribed in U.S. Pat. No. 3,051,697 there is obtained 25 parts of thedye of the formula ##STR195## 18.7 Parts of the above dye is quaternizedaccording to known processes such as, for example, those described inDOS No. 2,212,749 and 12.2 parts of a violet dye powder of the formula##STR196##are obtained which on polyacrylonitrile or on acid-modifiedpolyester fibres gives a fast reddish violet dyeing.

Using the coupling component of the formula ##STR197## and employing asimilar procedure, the dye of the formula ##STR198## is obtained, whichon polyacrylonitrile or on acidmodified polyester fibres gives fastdyeings of a reddish-violet shade.

The structural composition of further dyes is shown in the followingTable IV. The dyes can be prepared in accordance with the procedure ofthe foregoing Examples and agree with the formula ##STR199## in whichR₁, R₄, R₅, R₆, R₃ ' and Z₂ have the significances as shown in thecolumns of the table. The anion A.sup.⊖ may be any one of those named inthe foregoing description.

                                      TABLE IV                                    __________________________________________________________________________                                    Dye-shade on                                  Ex.                                                                              R.sub.1                                                                           R.sub.3 '                                                                          R.sub.4                                                                           R.sub.5                                                                           R.sub.6                                                                            Z.sub.2                                                                              polyacrylonitrile                             __________________________________________________________________________    144                                                                              H   CH.sub.3                                                                           H   H   C.sub.2 H.sub.5                                                                     ##STR200##                                                                          reddish-violet                                145                                                                              H   CH.sub.3                                                                           H   H   C.sub.2 H.sub.5                                                                     ##STR201##                                                                          "                                             146                                                                              H   CH.sub.3                                                                           H   H   C.sub.2 H.sub.5                                                                     ##STR202##                                                                          "                                             147                                                                              H   CH.sub.3                                                                           H   CH.sub.3                                                                          CH.sub.3                                                                            ##STR203##                                                                          "                                             148                                                                              H   CH.sub.3                                                                           H   CH.sub.3                                                                          CH.sub.3                                                                            ##STR204##                                                                          "                                             149                                                                              H   CH.sub.3                                                                           H   CH.sub.3                                                                          CH.sub.3                                                                            ##STR205##                                                                          "                                             150                                                                              H    CH.sub.3                                                                          CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                     ##STR206##                                                                          "                                             151                                                                              H   CH.sub.3                                                                           CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                     ##STR207##                                                                          "                                             152                                                                              CH.sub.3                                                                          CH.sub.3                                                                           H   H   C.sub.2 H.sub.5                                                                     ##STR208##                                                                          "                                             153                                                                              H   CH.sub.3                                                                           H   H   C.sub.2 H.sub.5                                                                     ##STR209##                                                                          violet                                        154                                                                              H   CH.sub.3                                                                           H   H   C.sub.2 H.sub.5                                                                     ##STR210##                                                                          "                                             155                                                                              H   C.sub.2 H.sub.5                                                                    H   H   C.sub.2 H.sub.5                                                                     ##STR211##                                                                          reddish-violet                                156                                                                              H   C.sub.2 H.sub.5                                                                    H   H   C.sub.2 H.sub.5                                                                     ##STR212##                                                                          "                                             157                                                                              H   OCH.sub.3                                                                          H   H   C.sub.2 H.sub.5                                                                     ##STR213##                                                                          "                                             __________________________________________________________________________

    __________________________________________________________________________                                             Dye-shade on poly-                   Ex.                                      acrylonitrile                        __________________________________________________________________________    158.                                                                              ##STR214##                           violet                               159.                                                                              ##STR215##                           blue                                 160.                                                                              ##STR216##                           blue                                 __________________________________________________________________________

Formulae of representative dyes of the foregoing Examples are asfollows: ##STR217##

What is claimed is:
 1. A compound of the formulawherein each R₁ and R₂is independently hydrogen; alkyl of 1 to 4 carbon atoms; alkyl of 1 to 4carbon atoms substituted by halo, alkoxy of 1 to 4 carbon atoms orphenoxy; phenyl or cycloalkyl of 5 to 6 carbon atoms, R₃ is hydrogen,phenyl, alkyl of 1 to 12 carbon atoms or alkyl of 1 to 12 carbon atomssubstituted by halo, alkoxy, cyano, phenyl, phenoxy, alkoxycarbonylwherein the alkoxy radical has 1 to 4 carbon atoms, alkylcarbonyloxywherein the alkyl radical has 1 to 4 carbon atoms, alkoxy of 1 to 4carbon atoms, benzoyloxy, --O--CO--N(Ra)₂ or --CO--N(RA)₂, wherein eachRa is independently hydrogen or alkyl of 1 to 4 carbon atoms, R₄ isalkyl of 1 to 8 carbon atoms; alkyl of 1 to 8 carbon atoms substitutedby halo, hydroxy, cyano, phenyl, phenoxy, cycloalkyl of 5 or 6 carbonatoms, alkoxy of 1 to 4 carbon atoms or carbamoyl; alkenyl of 2 to 8carbon atoms; alkenyl of 2 to 8 carbon atoms substituted by halo,hydroxy, cyano, phenyl, phenoxy, cycloalkyl of 5 to 6 carbon atoms,alkoxy of 1 to 4 carbon atoms or carbamoyl; alkoxy of 1 to 4 carbonatoms; alkoxy of 1 to 4 carbon atoms substituted by halo, hydroxy,cyano, phenyl, phenoxy, cycloalkyl of 5 to 6 carbon atoms, alkoxy of 1to 4 carbon atoms or carbamoyl; cycloalkyl of 5 or 6 carbon atoms;cycloalkyl of 5 or 6 carbon atoms substituted by alkyl of 1 to 4 carbonatoms or ##STR218## ##STR219## is triazolium, benzothiazulium ornaphthothiazolium, or a substituted derivative thereof, wherein eachsubstituent is independently alkyl of 1 to 4 carbon atoms; alkyl of 1 to4 carbon atoms substituted by phenyl, hydroxy, carbamoyl, cycloalkyl of5 to 6 carbon atoms, cyano or halo; halo; nitro; cyano; trifluoromethyl;alkoxy of 1 to 4 carbon atoms; alkoxy of 1 to 4 carbon atoms substitutedby phenyl, hydroxy, carbamoyl, cycloalkyl of 5 or 6 carbon atoms, cyanoor halo; cycloalkyl of 5 or 6 carbon atoms; cycloalkyl of 5 or 6 carbonatoms substituted by alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4carbon atoms or halo; phenyl; phenyl substituted by cyano, nitro, alkylof 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms or halo; phenoxy;phenoxy substituted by cyano, nitro, alkyl of 1 to 4 carbon atoms,alkoxy of 1 to 4 carbon atoms or halo; phenylazo; --CO--Ro; --CO--O--Ro;--CO--NH--Ro; --CO--N(Ro)₂ ; --NH--CO--Ro; --SO₂ --Ro; --SO₂ --NH--Ro;--SO₂ --N(Ro)₂ or --NH--SO₂ --Ro, wherein each Ro is independently alkylof 1 to 4 carbon atoms or phenyl, with the proviso that the azo group islinked to a carbon atom of the ring containing the quaternized nitrogenatom, B is phenylene, substituted phenylene having 1 or 2 substituents,naphthylene or substituted naphthylene having 1 or 2 substituents,wherein each substituent of substituted phenylene and substitutednaphthylene is independently alkoxy of 1 to 4 carbon atoms, alkyl of 1to 4 carbon atoms or halo, each Q is independently ##STR220## whereineach R is independently hydroxy; halo; alkyl of 1 to 4 carbon atoms;alkyl of 1 to 4 carbon atoms substituted by halo, hydroxy, cyano, phenylor phenoxy; alkoxy of 1 to 4 carbon atoms; alkoxy of 1 to 4 carbon atomssubstituted by halo, hydroxy, cyano, phenyl or phenoxy; trihalomethyl;trifluoromethyl; cycloalkyl of 5 or 6 carbon atoms; cycloalkyl of 5 or 6carbon atoms substituted by alkyl of 1 to 4 carbon atoms; cyano; nitro;phenoxy; naphthyloxy; phenylazo; --CO--Ro; --CO--O--Ro; --CO--NH--Ro;--CO--N(Ro)₂ ; --O--CO--Ro; --O--CO--NH--Ro; --O--CO--N(Ro)₂ ;--NH--CO--Ro; --SO₂ --Ro; --SO₂ --NH--Ro; --SO₂ --N(Ro)₂ ; --OSO₂--N(Ro)₂ ; ##STR221## wherein each Ro is independently alkyl of 1 to 4carbon atoms or phenyl, andX is --CO-- or --SO₂ --, and y is 0, 1, 2, 3,4 or 5, each x is independently 1, 2 or 3, and A.sup.⊖ is an anion,wherein each halo is independently chloro, bromo or iodo.
 2. A compoundaccording to claim 1 wherein eachR₁ is independently hydrogen, alkyl of1 to 4 carbon atoms or phenyl, R₂ is hydrogen, R₃ is hydrogen, alkyl of1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted byphenoxy, phenyl, alkoxycarbonyl wherein the alkoxy radical has 1 to 4carbon atoms or benzoyloxy, R₄ is alkyl of 1 to 4 carbon atoms, alkyl of1 to 4 carbon atoms substituted by phenyl, hydroxy or carbamoyl oralkoxy of 1 to 4 carbon atoms, ##STR222## is triazolium orbenzothiazolium, or a substituted derivative thereof, B is ##STR223## ornaphthylene, wherein R₇ ' is hydrogen, halo, alkyl of 1 to 4 carbonatoms or alkoxy of 1 to 4 carbon atoms, Q is ##STR224## or naphthyl,wherein y is 0, 1, 2, 3, 4 or 5, with the proviso that each R is halowhen y is 3, 4 or
 5. 3. A compound according to claim 2 wherein A.sup.⊖is chloride, ZnCl₃.sup.⊖, methylsulfate or acetate.
 4. A compoundaccording to claim 2 wherein ##STR225## is triazolium or substitutedtriazolium.
 5. A compound according to claim 2 wherein eachR₁ isindependently hydrogen, methyl or phenyl, R₂ is hydrogen, R₃ is methyl,ethyl, butyl, phenoxyethyl, benzyl, ethoxycarbonylethyl orbenzoyloxyethyl, R₄ is methyl, ethyl, benzyl, 2-hydroxyethyl,2-hydroxypropyl, 2-carbamoylethyl or methoxy, B is ##STR226## ornaphthylene, wherein R_(7a) is hydrogen, methyl, methoxy or chloro, Q is##STR227## or naphthyl, wherein eachR' is independently chloro, alkyl of1 to 4 carbon atoms, benzyl, nitro, cyano, phenylsulfonyl,methylsulfamoyl, dimethylsulfamoyl, trifluoromethyl, methoxycarbonyl,methylcarbamoyl, methoxy, phenoxy, benzoyloxy, phenylazo, benzamido,phenylcarbamoyloxy, dimethylcarbamoyloxy, N-methyl-n-phenylcarbamoyloxy,methylsulfonyl, dimethylsulfamoyloxy, phenoxymethyl, benzoyl or hydroxy,and y is 0, 1, 2, 3, 4 or 5, with the proviso that each R' is chloro ify is 3, 4 or 5, and x is 1 or
 2. 6. A compound according to claim 5 withthe proviso that each R' is chloro or one R' is hydroxy and the other isbenzoyl if y is 2 and each R' is chloro if v is 3, 4 or
 5. 7. A compoundaccording to claim 5 wherein ##STR228## is triazolium or substitutedtriazolium.
 8. A compound according to claim 7 having the formula##STR229## wherein R₁ " is hydrogen, methyl or phenyl,R₃ " is methyl,ethyl, butyl, ethoxycarbonylethyl or benzyl, R_(7a) is hydrogen, methyl,methoxy or chloro, each of R₈ " and R₉ " is independently methyl, ethyl,2-hydroxyethyl, 2-hydroxypropyl, 2-carbamoylethyl, benzyl, 2-phenylethylor cyclohexyl, Q"' is phenyl, naphthyl or phenyl substituted by methyl,chloro, methylsulfonyl or phenylsulfonyl, and A.sup.⊖ is an anion.
 9. Acompound according to claim 8 wherein R₁ " is hydrogen.
 10. A compoundaccording to claim 9 wherein each of R₃ ", R₈ " and R₉ " isindependently methyl, ethyl or benzyl.
 11. A compound according to claim10 whereinR₈ " is methyl, and R₉ " is methyl.
 12. A compound accordingto claim 8 wherein each of R₈ " and R₉ " is independently methyl, ethylor benzyl.
 13. A compound according to claim 1 having the formula##STR230## wherein P is ##STR231## wherein R₈ is alkyl of 1 to 4 carbonatoms; alkyl of 1 to 4 carbon atoms substituted by hydroxy, halo, cyano,phenyl or carbamoyl; alkenyl of 2 to 4 carbon atoms; alkenyl of 2 to 4carbon atoms substituted by hydroxy, halo, cyano, phenyl or carbamoyl;cyclohexyl or cyclohexyl substituted by alkyl of 1 to 4 carbon atoms,R₉is alkyl of 1 to 4 carbon atoms; alkyl of 1 to 4 carbon atomssubstituted by hydroxy, halo, cyano, phenyl or carbamoyl; cyclohexyl;cyclohexyl substituted by alkyl of 1 to 4 carbon atoms; phenyl or phenylsubstituted by halo, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4carbon atoms, R₁₀ is hydrogen or a significance of R₉, and each of R₁₆and R₁₇ is independently hydrogen; halo; alkyl of 1 to 4 carbon atoms;alkyl of 1 to 4 carbon atoms substituted by phenyl, hydroxy, carbamoyl,cycloalkyl of 5 or 6 carbon atoms, cyano or halo; alkoxy of 1 to 4carbon atoms; alkoxy of 1 to 4 carbon atoms substituted by phenyl,hydroxy, carbamoyl, cycloalkyl of 5 or 6 carbon atoms, cyano or halo;phenoxy; --CO--Ro; --CO--O--Ro; --CO--NH--Ro; --CO--N(Ro)₂ ;--NH--CO--Ro; --SO₂ --Ro; --SO₂ --NH--Ro; --SO₂ --N(Ro)₂ or --NH--SO₂--Ro, wherein each Ro is independently alkyl of 1 to 4 carbon atoms orphenyl, or R₁₆ and R₁₇ are on adjacent carbon atoms and taken togetherare --CH═CH--CH═CH--, each R₁ ' and R₂ ' is independently hydrogen,phenyl or alkyl of 1 to 4 carbon atoms, R₃ ' is hydrogen, alkyl of 1 to4 carbon atoms or alkyl of 1 to 4 carbon atoms substituted by phenyl,halo, alkoxy of 1 to 4 carbon atoms, phenoxy, alkylcarbonyloxy whereinthe alkyl radical has 1 to 4 carbon atoms, benzoyloxy, cyano ordialkylcarbamoyl wherein each alkyl radical independently has 1 to 4carbon atoms, B is ##STR232## or naphthylene, wherein R₇ ' is hydrogen,halo, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms, Q'is ##STR233## or naphthyl, wherein each R" is independently nitro; halo;hydroxy; cyano; trihalomethyl; trifluoromethyl; alkyl of 1 to 4 carbonatoms; alkyl of 1 to 4 carbon atoms substituted by phenyl or phenoxy;alkoxy of 1 to 4 carbon atoms; alkoxy of 1 to 4 carbon atoms substitutedby phenyl or phenoxy; phenoxy; phenylazo; cyclohexyl; benzoyloxy;phenylcarbamoyloxy; --CO--Ro; --CO--O--Ro; --CO--NH--Ro; --CO--N(Ro)₂ ;--NH--CO--Ro; --SO₂ --Ro; --SO₂ --NH--Ro; --SO₂ --N(Ro)₂ ;--O--CO--N(Ro)₂ ; --O--SO₂ --N(Ro)₂ ; ##STR234## wherein each Ro isindependently alkyl of 1 to 4 carbon atoms or phenyl, andX is --CO-- or--SO₂ --, and y is 0, 1, 2, 3, 4 or 5, with the proviso that each R" ishalo when y is 3, 4 or 5, x is 1, 2 or 3, and A.sup.⊖ is an anion.
 14. Acompound according to claim 13 wherein P is ##STR235##
 15. A compoundaccording to claim 14 whereinR₈ is alkyl of 1 to 4 carbon atoms or alkylof 1 to 4 carbon atoms monosubstituted by phenyl, hydroxy or carbamoyl,R₉ is alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atomsmonosubstituted by phenyl, hydroxy or carbamoyl, and R₁₀ is hydrogen,alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atomsmonosubstituted by phenyl.
 16. A compound according to claim 15whereinR₁ ' is hydrogen or alkyl of 1 to 4 carbon atoms, R₂ ' ishydrogen, R₃ ' is alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbonatoms monosubstituted by phenoxy, B is ##STR236## wherein R₇ " ishydrogen, alkyl of 1 to 4 carbon atoms or alkoxy of 1 to 4 carbon atoms,O' is ##STR237## or naphthyl, wherein each R''' is independently halo;nitro; cyano; phenylsulfonyl; alkoxy of 1 to 4 carbon atoms; benzoyl;phenoxy; benzoyloxy; phenylazo; benzamido; phenylcarbamoyloxy;trifluoromethyl; alkyl of 1 to 4 carbon atoms; alkyl of 1 to 4 carbonatoms monosubstituted by phenyl; --CO--O--Rz; --CO--NH--Rz; --SO₂ --Rz;--SO₂ --NH--Rz; --SO₂ --N(Rz)₂ ; --O--CO--N(Rz)₂ ; --O--CO--NRz--phenylor --O--SO₂ --N(Rz)₂, wherein each Rz is independently alkyl of 1 to 4carbon atoms, and y is 0, 1, 2, 3, 4 or 5, with the proviso that each R"is chloro if y is 3, 4 or 5, and x is
 1. 17. A compound according toclaim 16 wherein A.sup.⊖ is chloride, ZnCl₃.sup.⊖, methylsulfate oracetate.
 18. A compound according to claim 16 whereinR₈ is methyl, R₉ ismethyl, and R₁₀ is hydrogen.
 19. A compound according to claim 18whereinR₂ ' is hydrogen, R₃ ' is methyl or ethyl, R₇ " is hydrogen, andQ' is ##STR238## or 2-naphthyl, wherein eachR"" is nitro, cyano,phenylsulfonyl, methylsulfamoyl, dimethylsulfamoyl, methoxycarbonyl,methylcarbamoyl, methoxy, phenoxy, benzoyloxy, phenylazo, benzamido,phenylcarbamoyloxy, dimethylcarbamoyloxy, N-methyl-N-phenylcarbamoyloxy,methylsulfonyl, dimethylsulfamoyloxy, trifluoromethyl, methyl, benzyl orchloro, and y is 0, 1, 2, 3, 4 or 5, with the proviso that each R ischloro if y is 2, 3, 4 or
 5. 20. A compound according to claim 19 withthe proviso that when y is 1, R"" is in the 4-position.
 21. A compoundaccording to claim 19 wherein A.sup.⊖ is chloride, ZnCl₃.sup.⊖,methylsulfate or acetate.
 22. A compound according to claim 13 wherein Pis ##STR239##
 23. A compound according to claim 22 whereinR₈ is alkyl of1 to 4 carbon atoms or alkyl of 1 to 4 carbon atoms monosubstituted bycarbamoyl, and each of R₁₆ and R₁₇ is independently hydrogen; alkoxy of1 to 4 carbon atoms; alkoxy of 1 to 4 carbon atoms monosubstituted byphenyl; benzamido; phenoxy; phenylsulfonyl; --CO--Rz; --CO--NH--Rz or--NH--SO₂ --Rz; wherein each Rz is independently alkyl of 1 to 4 carbonatoms, or R₁₆ and R₁₇ are on adjacent carbon atoms and taken togetherare --CH═CH--CH═CH--.
 24. A compound according to claim 23 whereinR₁ 'is hydrogen or methyl, R₂ ' is hydrogen, R₃ ' is methyl or ethyl, B is##STR240## wherein R₇ "" is hydrogen or methyl, Q' is ##STR241## ornaphthyl, wherein y is 0, 1, 2, 3, 4 or 5, and x is
 1. 25. A compoundaccording to claim 22 having the formula ##STR242## wherein R₁ "' ishydrogen or methyl,R₃ "' is methyl or ethyl, R_(7a) is hydrogen, methyl,methoxy or chloro, R₈ "' is methyl, ethyl, 2-hydroxyethyl,2-hydroxypropyl or 2-carbamoylethyl, R₁₆ " is hydrogen, methyl, methoxy,phenoxy, benzyloxy, acetamido, methylsulfonylamino or benzamido, R₁₇ "is hydrogen or methyl or R₁₆ " and R₁₇ " taken together are--CH═CH--CH═CH--, Q_(a) "' is phenyl, naphthyl or phenyl substituted bychloro or methyl, and A.sup.⊖ is an anion.
 26. A compound according toclaim 25 whereinR₁₆ " is methoxy, and R₁₇ " is methyl.
 27. A compoundaccording to claim 25 whereinR₁ "' is hydrogen, R₈ "' is methyl orethyl, and R₁₆ " is methoxy.
 28. A compound according to claim 13 havingthe formula ##STR243## wherein P' is ##STR244## wherein R₅₃ is hydrogen,methyl, phenyl or benzyl,each of R₅₄ and R₅₅ is independently alkyl of 1to 4 carbon atoms or alkyl of 1 to 4 carbon atoms monosubstituted byhydroxy or carbamoyl, R₅₇ is hydrogen or alkoxy of 1 to 4 carbon atoms,and R₅₉ is alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbon atomsmonosubstituted by carbamoyl, R₅₀ is alkyl of 1 to 4 carbon atoms oralkyl of 1 to 4 carbon atoms monosubstituted by phenyl, R₅₁ is hydrogenor alkyl of 1 to 4 carbon atoms, B is ##STR245## wherein R₇ "' ishydrogen or alkyl of 1 to 4 carbon atoms, Q is ##STR246## or naphthyl,wherein eachR^(vi) is independently hydroxy, halo, alkoxycarbonylwherein the alkoxy radical has 1 to 4 carbon atoms, phenoxy, benzoyl,cyclohexyl, alkyl of 1 to 4 carbon atoms, alkyl of 1 to 4 carbon atomsmonosubstituted by phenyl or trihalomethyl, and Y is 0, 1, 2, 3, 4 or 5,with the proviso that each R^(vi) is halo when y is 3, 4 or 5, andA.sup.⊖ is an anion.
 29. A compound according to claim 28, whereinA.sup.⊖ is chloride, ZnCl₃.sup.⊖, methylsulfate or acetate.
 30. Acompound according to claim 28 wherein P' is ##STR247##
 31. A compoundaccording to claim 28 wherein P' is ##STR248##
 32. A compound accordingto claim 28 having the formula ##STR249## wherein R_(50a) is alkyl of 1to 4 carbon atoms,R_(51a) is hydrogen or methyl, each of R₅₄ and R₅₅ isindependently alkyl of 1 to 4 carbon atoms or alkyl of 1 to 4 carbonatoms monosubstituted by hydroxy or carbamoyl, Q_(1a) " is methylphenyl,dimethylphenyl, ##STR250## 3-hydroxy-4-benzoylphenyl or naphthyl,wherein y is 0, 1, 2, 3, 4 or 5, and A.sup.⊖ is an anion.
 33. A compoundaccording to claim 32 wherein A.sup.⊖ is chloride, ZnCl₃.sup.⊖,methylsulfate or acetate.
 34. A compound according to claim 33, havingthe formula ##STR251##
 35. A compound according to claim 34 whereinA.sup.⊖ is ZnCl₃.sup.⊖.
 36. A compound according to claim 33 having theformula ##STR252##
 37. A compound according to claim 33 having theformula ##STR253##
 38. A compound according to claim 33 having theformula ##STR254##
 39. A compound according to claim 33 having theformula ##STR255##
 40. A compound according to claim 39 wherein A.sup.⊖is ZnCl₃.sup.⊖.
 41. A compound according to claim 33 having the formula##STR256##
 42. A compound according to claim 41 wherein A.sup.⊖ isZnCl₃.sup.⊖.
 43. A compound according to claim 32 having the formula##STR257## wherein A.sup.⊖ is an anion.
 44. A compound according toclaim 33 having the formula ##STR258## wherein A.sup.⊖ is an anion. 45.A compound according to claim 35 having the formula ##STR259## whereinA.sup.⊖ is an anion.
 46. A compound according to claim 32 having theformula ##STR260## wherein A.sup.⊖ is an anion.
 47. A compound accordingto claim 28 having the formula ##STR261## wherein A.sup.⊖ is an anion.48. A compound according to claim 28 having the formula ##STR262##wherein A.sup.⊖ is an anion.
 49. A compound according to claim 29 havingthe of formula ##STR263##